Vinyl ester resins and process of making same



Patent edAug. 20, 1 929. n i

" UNITED STATES PATENT oFrIfc HOWARD wQMA rEEsoN, or MONTREAL, QUEBEC, AND FREDERICK w. sxrmnow, orsHAWIN GA FALLS, QUEBEC, CANADA ASSIGNORS' 'ro oaNaDmN ELEcrEo rnomrors COMPANY, LIMITED, F MONTREAL, CANADA.

VINYL Es'rEE RESINS AND PROCESS OF MIAKING SAME No Drawing. Application filed August 15, 1927. Serial No. 218,208.

.This invention relates broadly to the man vention but it will be understood that the 50 ul'acture of synthetic gummy or resinous mainvention is not limited to these examples or tcri'als obtained by the interaction or treatto theroportions, materials or conditions ment of bodies containing an ethylene linkset fort i. in the examples 5 age with saturated aliphatic aldehydes or E Z I aldehydic bodies, and relates more particuv wan-n? e e 5 larly to the manufacture of products by One-tenthof one art ofacetaldeh de or treatment of vinyl compounds, especially slightly less is added to 100'parts 0 vinyl vinyl esters, with aldehydes. acetate (by volume), and the mixture placed 2o In a prior application, Serial No. 147,183, in a bomb where it is heated for approxililed the 8th November 1926, there is (16- mately sixteen hours at a. temperature of ap- 0 scribed a process of the foregoing character. proximately 100 C. Unchanged Vinyl ester The disclosure of this prior application is, and any unchanged aldehyde that may 1'0 llUWCVGl', t0 the treatment Of vinyl nmjn are, eparated fro n the product disesters with aldehydes and the proportions tillation in an suitable Way, and about 66,

given in the examples are ten to fifteen parts rt f a r c will be obtained which is ofaldehyde to 100 parts of vinyl ester. The h d wh old but of a, tough, rubbery reaction is stated tlo be slow at OIEllHELI'y temconsistency h wamL I )eratures and wit iout pressure at to occur V 20 inore rapidly under heat and pressure.

According to the present invention, bodies P o di as i Ex mple I but using containing an ethylene linkage, hereinafter from 1 to 5 parts of acetaldehyde to 100 generally referred .to as .vinyl compounds, -t f i l tate, approxunately Q5 76 I'UELCt-Qtl 0]. tl'Qfl-ttjd \Vltll saturated Elllparts of product wi] -be btained wh ch. 's 26 phatic aldehydes or aldehydic bodies, hereli htl ft th th t lting from th after generally designated by tle tp l g process of Example I. dch 'l'les. The reaction procee s s ow y a ordinary atmospheric temperature and preswampze f sure but, by application of heat and super- P di as i E l I 'but using :0 atmospheric pressure, the reaction is greatly f 10 t 15 a -t f ld hyd to 100 parts accelerated and the desired products obtained f Vinyl acetate, between 90 and arts f r in commercial quantities in from six six- Product is Obtained which is hard w en d teen hours or more if a large proport on of but, h warmed to b d t m 5 aldehyde is present. The consistencyof-the tens to readily kneadayyle an d t l 35 Product Varies according the P P F dition of about the consistencyof ordmary of aldehyde used, those bodies made with a chewing gum and. which has a capaclty f small proportion of aldehyde beingnormaltaking up a certam amount f water 1y hard or tough and rubbery, while those Emam 16 IV made with larger proportions of aldehyde P V v 40 are gummy or sticky and semi-liquid or liq- Proceeding, as i E l I b t 100 uid, acco ding as the p opo tion of aldehyde parts of acetaldehyde to 190 vWLI'tiOf ymyl is increased. The presence of orygen seems acetate, -there results after dlstluatlol} to have desirable effect on the yield and ra-- proximately 12 Parts of a Product thwh 1S pidity of the action. Son c oxygen may be Soft and stick If larger proportlons of I taken up during the reaction but the presaldehyde are used, softer Products are ence of oxygen, although desirable, does not mined. seem to'be entirely neclessar t nus f llowin exam es W1 serve o 1 tr tii vai'ious miithods 81: carrying out the m- 100 parts of vmylformate 1s treated wlth Emamp le Y.

acetaldehyde in proportions according to the'preceding examples and with approximately similar results.

Example VI.

- given in the examples, products may be obtained using vinyl butyrate and vinyl esters of higher molecular weight, also various aldehydes, such as butyraldehyde and aldehydes of higher molecularweight, may be used. The process may also be conducted substituting vinyl ethers, vinyl halides or other ethylene linkage bodies for the vinyl esters. The term aldehydic bodies hereinbefore used designates such bodies as will liberate an aldehyde during progress of the reaction, for example, paraldehyde, and more particularly if a, trace of mineral acid is present which serves to decompose the paraldehyde. In the sameway, bodies of the acetal type may be utilized under conditions such that they will liberate aldehyde.

It is necessary in carrying out the process that .the materials used be of a certain degree ofpurity, since the presence of certain impurities has detrimental eflect on the reaction or may completely inhibit the reaction. Sulphur and certain of its compounds are bodies which inhibit reaction and iron or copper and certain compounds thereof have detrimental effect. For this reason, it is important to avoid the use of iron or copper apparatus. The process may be conducted satisfactorily in vessels of glass, porcelain, enamel or aluminum.

The carrying out of the process is not confined to the bombing treatment but may be carried out by heatin the reaction mixture under a reflux con enser, the time of reaction being'considerably increased by such. a procedure.

While the in the examples are sixteen hours and 100, it will be understood that many -variations in time and temperature may beinade and desirable results obtained. Reaction to a commercial extent may sometimesbe obtained in six hours or less and, especially when lower temperatures are employed, the time of reaction may be extended to days or 3 evenweeks. The temperature may vary between ordinary room temperature, say 25 0., and as much above 100 as it is possigo without 'occasionmg undesirable uents of. the reaction mixture. The pressure may also be varied as desired. For instance, using 10 to 15 parts of acetaldehyde to 100 parts of vinyl acetate at atmospheric time and temperature disclosedtemperature and pressure, the reaction will proceed slowly and will take several weeks to go to completion.

It will be understood that, while the pro-' portions givenin the examples range between one-tenth of one'part and 100 parts of aldeliyde to 100 parts of vinyl compound, the invention is not confined to this range.

: Having thus described our invention, what we' claim is Y 1. A process of making gummy or resinous products, which comprises reacting together a body containing an ethylene hnkage and a saturated aliphatic aldehyde.

2. A process of making gummy or resinous products, which comprises reacting together a. body containing an ethylene linkage and ing and under pressure.

3. A process of making gummy or resinous products, which comprises reacting together a vinyl ester and a saturated aliphatic aldehyde.

4. A process of making gummy or resinous products, which comprises reacting together a vinyl ester and acetaldehyde.

5. A process of making gummy or resinousmaterials, which comprises reacting together vinyl acetate and a saturated aliphatic aldehyde.

6. A process of making gummy or resinous products, which comprises reacting together vinyl acetate and acetaldehyde.

. 7. A process of making gummy or resinous products which comprises reacting together a body containing an ethylene linkage and a saturated aliphatic aldehyde in presence of oxygen.

8. A process of making gummy or resinous products, which comprises reacting together a body containing an ethylene linkage and a saturated aliphatic aldehyde with heating and under pressure in presence of oxygen.

9. Aprocess of making gummy or resinous products, which comprises reacting together 100 parts of a body containing an ethylene linkage and one-tenth of one part to upwards of 100 parts of a saturated aliphatic aldehyde. I

10. A composition of matter resulting from reacting together a body containing an a saturated aliphatic aldehyde with heat- 7 ethylene linkage and a'saturated aliphatic aldehyde.

'11. A composition of matter resulting from reacting together a body containing an ethylene linkage and a saturated aliphatic aldehyde with heating and under pressure.

from reacting together a vinyl ester and a saturated aliphatic. aldehyde.

13. A composition of matter resulting -from reacting together a vinyl ester and acetaldehyde.

-12. A composition of matter resulting 14, A composition of matter resulting from reacting together vin 1 acetate and a saturated aliphatic aldehy e.

15. A composition of matter resulting 5 from reacting together'vi'nyl acetate and acetaldehyde.

16. A composition of matter resulting from reacting together a body containing an ethylene linkage and a saturated aliphatic 10 aldehyde in presence of oxygen.

17 A composition of matter resulting from reacting together a body containing an ethylene linkage and a saturated aliphatic aldehyde with heating and under pressure in presence of oxygen.

18. A composition of matter resulting from reacting together 100 parts of a body containing ethylene linkage and one-tenth of one part to upwards of 100 parts of a saturated aliphatic aldehyde.

In witness whereof, we have hereunto set our hands.

HOWARD W. MATHESON. FREDERICK W. SKIRROW. 

